JPH0233756B2 - - Google Patents

Description

[Detailed description of the invention]

Distillate fuel oil processing additive systems for improving the flow of waxy fuel through pipelines and filters in cold climates are known as shown in the following patents: US Pat. British Patent Nos. 900202 and 263152 relate to the use of low molecular weight copolymers of ethylene and unsaturated esters, particularly vinyl acetate, while British Patent No. 1374051 raises the onset temperature of wax crystallization and It concerns the use of additive systems to limit the size of wax crystals. The use of low molecular weight copolymers of ethylene and other olefins as pour point depressants in distillate fuels is described in British Patent No. 848777, no.
No. 993744, No. 1068000 and U.S. Patent No.
It is described in the specification of No. 3679380. U.S. Patent No. 3374073, No. 3499741, No. 3507636, No.
Various other special types of polymers are suggested as additives for distillate fuels in US Pat. It has also been proposed that additive formulations may be used in distillate fuels to further improve their flow and pour point properties. For example, US Pat. No. 3,661,541 relates to the use of blends of ethylene/unsaturated ester copolymer type additives with the low molecular weight ethylene propylene copolymers of UK Patent No. 993,744. U.S. Pat. No. 3,658,493 teaches various nitrogen salts and amides of acids such as monocarboxylic, dicarboxylic, phenolic, and sulfonic acids in combination with ethylene mono- or copolymer pour point depressants for middle distillate oils. There is. U.S. Pat. No. 3,982,909 discloses that nitrogen compounds, such as ammonium salts of amides, diamides, and monoamides or monoesters of dicarboxylic acids, alone or in petroleum-derived microcrystalline waxes and/or pour point depressants, particularly those with an ethylene backbone. In combination with polymeric pour point depressants, it is taught to be a wax crystal modifier and cold flow improver for middle distillate fuel oils, particularly diesel fuels. US Patent Nos. 3,444,082 and 3,946,093 teach the use of various alkenylsuccinic anhydride amides and amine salts in combination with ethylene copolymer pour point depressants for distillate fuel applications. The above additives are generally used to lower the pour point of distillate fuels by preventing gelation of the oil by wax crystals and/or to lower the pour point of wax-containing oils by reducing the size of wax crystals. have been used to improve flow through filters. Although it is important to obtain these effects, it is desirable to further reduce the crystal size,
There is also the problem that in oils with improved pour point and flow properties, wax crystals that form during storage of the oil in cold climates settle and agglomerate, creating distribution problems. Since there is a large amount of oil in the storage tank, even if the surrounding temperature is well below the oil's cloud point (the temperature at which wax becomes visible, i.e., the oil begins to cloud), the overall temperature of the oil gradually decreases. decreases to
When winters are particularly cold and long, and oil is stored in extremely cold climates for long periods of time, the temperature of the stored oil will eventually drop below its cloud point, even in large commercial tanks. there is a possibility. Under these conditions, wax agglomeration may then occur, further enhancing wax agglomeration as a dense wax concentrate collects at the bottom of the tank. The inventors have found that it is possible to significantly reduce these problems through the use of certain additive formulations. The inventors have also found that under certain conditions the use of these additive formulations can provide better control of crystal size than the same concentration of conventional additives. Therefore, the present invention provides substances of the following classes (A), (B) and (C): (A) a composition for improving distillate oil flow; (B) a number average molecular weight of 10 ³ or more, preferably 10 ⁴ or more high molecular weight hydrocarbon polymers or derivatized versions thereof, and (C), unlike (A) and (B), contain polar oil-soluble compounds of formula RX as described below. An additive formulation is provided. The inventors have demonstrated that the additive formulation of the present invention
It has been found to be particularly useful in controlling the growth and agglomeration of separating waxes in distillate fuel oils with boiling points in the range of ~500°C, especially 160°C to 400°C.
Accordingly, the present invention also provides such distillate fuel oils containing such additive formulations. The total additive content in the fuel is from 0.001 to 1.0% by weight, preferably from 0.001 to 0.5%, such as from 0.005 to 0.2%, more preferably from 0.01 to 0.2%, most preferably from 0.005 to 0.05%, such as from 0.02 to It is 0.1% by weight. It consists of a blend of (A), (B) and (C), each of which can be present in an amount of 0.1 to 10 parts by weight relative to each other. The additive formulation of the present invention comprises 1 part by weight of distillate flow improving composition (A);
It is preferred to contain 0.1 to 10 parts by weight, preferably 0.2 to 2 parts by weight of the hydrocarbon polymer (B), and 0.1 to 10 parts by weight, preferably 0.2 to 1 part by weight of the polar oil-soluble compound (C). Due to ease of handling, additives are generally
It is supplied as a concentrate containing 90% by weight, preferably 30-80% by weight of hydrocarbon diluent, the remainder being additives. The invention also relates to such concentrates. The distillate flow improver A used in the additive formulation of the present invention is a wax crystal growth arrester and may also contain nucleation products for wax crystals as described in GB 1374051. can. Such growth inhibitors and nucleating agents are preferably wax crystal modifiers for distillate fuel oils, such as ethylene polymers of the type known in the art as pour point depressants and cold flow improvers. These polymers have a polymethylene backbone that is segmented by hydrocarbon or oxyhydrocarbon side chains, alicyclic or heterocyclic structures, or chlorine atoms. These polymers can be homopolymers of ethylene produced by free radical polymerization;
There may be some branching. Furthermore, these polymers usually contain a second ethylenically unsaturated monomer as defined below and which may be a single monomer or a mixture of monomers in any proportion. The copolymer contains about 3 to 40 molar ratios, preferably 4 to 20 molar ratios, per molar ratio of copolymer. This polymer can be used by vapor pressure osmotic
The number average molecular weight as measured by osmometry (VPO) is generally in the range from 500 to 50,000, for example from 500 to 10,000, preferably from 1,000 to 6,000. The unsaturated monomer copolymerizable with ethylene has the general formula [In the above general formula, R ₁ is hydrogen or methyl, and R ₂ is -OOCR ₄ group (here, R ₄ is hydrogen or C _1
-C28 , more usually _C1 - _C17 , preferably _C1-
C ₈ straight or branched alkyl group) or R ₂ is a −COOR ₄ group (where R ₄ is as previously defined but not hydrogen) and R ₃ is unsaturated mono- and diesters of hydrogen or -COOR ₄ as previously defined. R ₁
and when R ₃ is hydrogen and R ₂ is -OOCR ₄ the monomer is a C ₁ -C ₂₉ , more usually C ₁ -C ₁₈ monocarboxylic acid, preferably a C ₂ -C ₅ monocarboxylic acid. Contains vinyl alcohol esters of monocarboxylic acids. Examples of such esters include vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate and vinyl palmitate, with vinyl acetate being the preferred ester. When _R2 is _-COOR4 and _R3 is hydrogen, such esters include methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, _C13 oxo alcohol ester of methacrylic acid, and the like.
Examples of monomers in which R ₁ is hydrogen and R ₂ and R ₃ are -COOR ₄ groups include mono- and diesters of unsaturated dicarboxylic acids, such as fumaric acid mono-C ₁₃
Includes oxo, _diC13 oxo fumarate, diisopropyl maleate, dilauryl fumarate, and ethylmethyl fumarate. In the case of monoester,
The remaining carboxyl group is reacted with an amine to yield the amine salt or amide of the hemiester. Another group of monomers that can be copolymerized with ethylene includes _C3 - _C30 , preferably _C3 - _C18 alpha-monoolefins, which include propylene, isobutene, It may be branched or linear, such as n-octene-1, iso-octene-1, n-decene-1, dodecene-1, etc. Still other monomers include vinyl chloride, but essentially the same results may be obtained, for example, with chlorinated polyethylene having a chlorine content of up to about 35% by weight. Some distillate flow improvers include U.S. Pat.
Also included are hydrogenated polybutadiene flow improvers made primarily by 1,4 addition and partially by 1,2 addition as described in US Pat. No. 3,600,311. Preferred ethylene copolymers are ethylene vinyl ester copolymers, especially vinyl acetate copolymers. These copolymers can be prepared at high pressure in the presence or absence of a solvent. When copolymerization is carried out in solution, the solvent and 5 to 50% by weight of the total amount of monomers other than ethylene are charged into a stainless steel pressure vessel equipped with a stirrer and a heat exchanger. The temperature of the pressure vessel is then brought to the desired reaction temperature, e.g. 70-200°C, while at the same time the autoclave is heated with ethylene to the desired pressure, e.g.
~1757.5Kg/cm ² gauge pressure (700~25000psig) Normal
Pressurize to 63.27-492.1Kg/cm ² gauge pressure (900-7000psig). Typically, the initiator diluted (or dissolved if solid) in the polymerization solvent is injected during the polymerization, and additional amounts of monomer charges other than ethylene, such as vinyl esters, are added continuously or at least periodically during the reaction period. pump into the container. During this reaction period, as ethylene is consumed in the polymerization reaction, additional ethylene is fed through a pressure regulator so that the desired reaction pressure remains fairly constant. The copolymerization temperature is kept approximately constant by a heat exchanger. After the reaction has ended, the liquid phase is discharged from the reactor, although a total reaction time of 1/4 to 10 hours is usually sufficient. The solvent and other volatile components in the reaction mixture are stripped off to yield a copolymer as a residue. For ease of handling and formulation, the polymer is generally dissolved in an aromatic solvent such as mineral oil, preferably heavy aromatic naphtha, and
It is usually made into a concentrate containing 10-60% by weight of copolymer. Initiators can decompose at high temperatures to give free radicals, such as acyl peroxides of _C2 to _C18 branched or straight chain carboxylic acids, as well as peroxides or azo-type initiators, including conventional initiators. selected from the group of compounds.
Particular examples of such initiators include dibenzoyl peroxide, ditertiary butyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, t-butyl hydroperoxide, α,α'-azo-diisobutyro Contains nitrile, dilauroyl peroxide, etc. The choice of peroxide is primarily governed by the polymerization conditions used, the desired polymer structure and the efficiency of the initiator. T-butyl peroctoate, dilauroyl peroxide and di-t-butyl peroxide are preferred initiators. The high molecular weight oil-soluble hydrocarbon "B", preferably the olefin copolymer, has a number average molecular weight of 10 ³ as determined by gel permeation chromatography or more preferably by membrane osmometry. ~10 ⁶ , preferably
10 ⁴ to 10 ⁶ , preferably 20000 to 250000, more preferably 20000 to 150000, most preferably 50000 to
Must be 150000 or 10000-50000.
Examples of suitable hydrocarbon polymers include C ₂ -C olefins, including both α-olefins and internal olefins, which can be linear or branched aliphatic, aromatic, alkyl aromatic, cycloaliphatic, etc. ₃₀ , e.g. C ₂
- Homopolymers and copolymers of two or more monomers of _C8 olefins are included. Often these polymers are polymers of ethylene and _C3 - _C30 olefins, particularly preferred are copolymers of ethylene and propylene, and polymers of propylene and other olefins such as butene and preferably polyisobutylene. be. Homopolymers and copolymers of C ₆ or higher α-olefins can also be preferably used. Such hydrocarbon polymers also include olefin polymers, hydrogenated polymers and copolymers, such as atactic polypropylene, and terpolymers of styrene with, for example, isoprene and/or butadiene. The polymer can be reduced in molecular weight, for example by mastication, extrusion, oxidation or pyrolysis, and can also be oxidized to contain oxygen. Derivatized polymers, such as post-grafted interpolymers of ethylene-propylene and active monomers such as maleic anhydride, which can be further reacted with alcohols or amines, such as alkylene polyamines or hydroxyamines. (For example, U.S. Patent No.
4089794, 4160739, 4137185) or US Pat. No. 4068056, 4068058
Also included are derivatized polymers, such as copolymers of ethylene and propylene reacted or grafted with nitrogen compounds, as shown in Nos. 4,146,489 and 4,149,984. The oil-soluble polymer may also be a viscosity index improver. Preferred hydrocarbon polymers of the invention include 15 to 90% by weight of ethylene, preferably 30 to 80% by weight of ethylene and 10 to 85% by weight of ethylene.
% by weight, preferably 20-70% by weight of one or more
_C3 to _C28 , preferably _C3 to _C18 , more preferably
It is an ethylene copolymer containing _C3 to _C8 α-olefin. Although not essential, it is preferred that such copolymers have a crystallinity of 25% by weight or less as measured by X-ray and differential scanning calorimetry. Most preferred are copolymers of ethylene and propylene. Other α-olefins suitable for use in place of propylene to form copolymers or for blending ethylene and propylene to form terpolymers, tetrapolymers, etc. include 1-
Includes butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc., 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene. -1,
Also included are branched α-olefins such as 4,4-dimethyl-1-pentene, 6-methylheptene-1, etc., as well as mixtures thereof. Terpolymers, tetrapolymers, etc. of ethylene, the _C3-28 α-olefins described above, and non-conjugated diolefins or mixtures of such diolefins can also be used. The amount of non-conjugated diolefin ranges from about 0.5 to 20 mole percent, preferably from about 1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin present. Representative examples of non-conjugated dienes that can be used as the third monomer in the terpolymer include linear non-cyclic dienes such as a 1,4-hexadiene; 1,5-heptadiene; 1,6-octadiene; Formula diene, b 5-methyl-1,4-hexadiene; 3,7
-dimethyl-1,6-octadiene; 3,7-
branched acyclic dienes such as dimethyl-1,7-octadiene; and mixed isomers of dihydromircene and dihydrocymene, c 1,4-cyclohexadiene; 1,5-cyclooctadiene; 1,5 -Cyclodecadiene; 4-vinylcyclohexene; 1-allyl-
4-isopropylidenecyclohexane; 3-allyl-cyclopentene; monocyclic alicyclic dienes such as 4-allylcyclohexene and 1-isopropenyl-4-(4-butenyl)cyclohexane, d4,4'-dicyclopentenyl and 4,4'-
Polymonocyclic alicyclic dienes such as dicyclohexenyldiene; Methyl-2-norbornene, 5-methylene-6,6-dimethyl-2-norbornene, 5-propenyl-2-norbornene, 5-(3-cyclopentenyl)-2
-norbornene and 5-cyclohexylidene-2-norbornene; alkyl, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene; polycyclic alicyclic fused and bridged ring dienes such as norbornadiene and the like. Among the above, preferred representative diolefins include cyclopentadiene, 2-methylene-5-norbornene, non-conjugated hexadiene, or other cycloaliphatic or aliphatic non-carbon atoms having from 6 to 15 carbon atoms per molecule. Conjugated diolefins, such as 2-methyl or ethylnorbornadiene, 2,4-dimethyl-2-octadiene, 3-(2-methyl-
(1-propene) cyclopentene, ethylidene norbornene, etc. Terpolymers, tetrapolymers, etc. useful in the present invention include 30 mole % or more, preferably 85 mole % or less ethylene; about 15 to about 70 mole % higher alpha-olefins or mixtures thereof, preferably propylene; and 1 It is preferred to contain from 20 mol %, preferably from 1 to 15 mol %, of a non-conjugated diene or mixture thereof. Particularly preferred are polymers of about 40 to 70 mole percent ethylene, 20 to 58 mole percent higher moreolefins, and 2 to 10 mole percent dienes. On a weight basis, the diene typically represents at least 2 or 3% by weight of the total terpolymer. Polyisobutylene is prepared by polymerizing isoolefins such as isobutylene in the presence of suitable Friedel-Crafts catalysts such as boron fluoride, aluminum chloride, etc. at temperatures substantially below 0°C, such as -40°C. It can be easily obtained by a known method such as the method described in No. 2084501. Such polyisobutylene is disclosed in U.S. Pat.
2,534,095 with higher linear α-olefins of 6 to 20 carbon atoms, in which case the resulting copolymer contains about 75 to about 99 volume percent isobutylene and 6 to 20 carbon atoms. from about 1% to about 25% by volume of higher normal alpha-olefins of carbon atoms. These ethylene copolymers (the term includes terpolymers, tetrapolymers, etc.) can be produced using known Ziegler-Natsuta catalysts as described in British Patent No. 1,397,994. Such polymerizations to produce ethylene copolymers include from 0.1 to 15 parts, such as 5 parts of ethylene;
10 parts, e.g. 2.5 parts of the above-mentioned higher α-olefin,
Typically propylene; and 10 to 10,000 parts of hydrogen per million parts of ethylene; (a) about 0.0017 to 0.017
part, e.g. 0.0086 part of transition metal main catalyst, e.g.
VOCl ₃ and (b) 0.0084 to 0.084 parts, e.g. 0.042 parts of a cocatalyst, e.g. (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ in 100 parts of an inert liquid solvent at a temperature of about 25° C. and 4.218
This can be carried out at Kg/cm ² gauge pressure (60 psig) for a period sufficient to obtain optimum conversion, such as from 15 minutes to 30 minutes. All parts above are parts by weight. Other suitable hydrocarbon polymers can be made from styrene and substituted styrenes such as alkylated or halogenated styrenes.
The alkyl group of the alkylated styrene can be a substituent on the aromatic ring or on the alpha carbon atom, with 1
It can contain up to about 20 carbon atoms, preferably 1 to 6 carbon atoms. These styrenic type monomers can be copolymerized with suitable conjugated diene monomers, including butadiene and alkyl-substituted butadienes in which the alkyl substituents have from 1 to about 6 carbon atoms. Thus, in addition to butadiene, isoprene, piperylene and 2,3-dimethylbutadiene are useful as diene monomers. Interpolymers can be produced by polymerizing two or more different styrenic monomers as well as two or more different conjugated diene monomers. Still other useful polymers can be derived without styrene, solely from aliphatic conjugated dienes, usually having 4 to 6 carbon atoms, most usefully from butadiene.
For example, 1,3-butadiene, isoprene, 1,3
- homopolymers of pentadiene, 1,3-dimethylbutadiene, copolymers made of at least two of these conjugated dienes and copolymers of the latter with styrene, homopolymers and copolymers thereof; is hydrogenated. It is preferred that these above-mentioned polymers having significant unsaturation be completely hydrogenated to remove nearly all olefinic unsaturation, although in some cases partial hydrogenation of aromatic type unsaturation will occur. These interpolymers are prepared by conventional polymerization techniques, including the preparation of interpolymers having controlled types of configurations of the polymerizing monomers, ie, random, block, tapered, etc. configurations. Hydrogenation of the interpolymer is carried out using conventional hydrogenation methods. One separate subclass of class (B) is the grafting of maleic anhydride onto the polymer, followed by amination or phosphoro-sulfurization.
derivatized to contain polar groups by These hydrocarbon polymers can be grafted with other monomers such as pyridine. Polar compound (C), unlike (A) and (B), is generally a monomer and may be ionic or nonionic. It is believed that this compound further inhibits wax crystal agglomeration by being adsorbed on the wax crystal faces with its hydrocarbon portion. Suitable compounds of class "C" can be nonionic or ionic, and if ionic, can be monofunctional or polyfunctional anions and cations. Monofunctional, oil-soluble, ionic or non-ionic compounds can be represented by the formula R ₅ X, and salts can be represented by the formula
It can be shown as R ₅ XZR ₆ . Here, R ₅ is an oil-soluble group and X is a polar group. R ₅ can be a monosubstituted or more substituted or unsubstituted, saturated or unsaturated hydrocarbon radical, which can be aliphatic, cycloaliphatic or aromatic, preferably alkyl, alkaryl or alkenyl. and most preferably R ₅ is saturated. R ₅ preferably contains a total of 8 to 150 carbon atoms.
If compound RX is nonionic, R ₅ is 14
Contains ~60 carbon atoms, more preferably 16-40
Preferably, it contains 5 carbon atoms. When R ₅ X is an anion, R ₅ has 8 to 150 carbon atoms,
More preferably it contains 12 to 50 carbon atoms, most preferably 14 to 40 carbon atoms. Particularly preferably the alkyl group contains 1 to 35 carbon atoms, most preferably 12 to 30 carbon atoms. When R ₅ consists of an alkyl group, the alkyl group is preferably linear. or,
R ₅ may be an alkyloxylated chain. Examples of suitable polar groups X include carboxylate COO
- group, sulfonate SO ₃ - group, sulfate OSO ₃ - group,
Included are phosphate O ₂ PO ₂ - groups, carbonate Pho - groups and borate O ₂ BO - groups. Thus, preferred anions of the invention include _R7COO- , _{R7SO3- ,}
R ₇ OSO ₃ −, (R ₇ O) ₂ PO ₂ −, R ₇ PhO−,
( _R7O ) _2BO- , where _R7 is an oil-soluble hydrocarbon group, and the total carbon atom content of _R7 is within the limits listed above for _R5 . When the anion is a sulfonic acid, preference is given to using an alkaryl sulfonate, which can be any of the known neutral or basic sulfonates. When the anion is a carbonate, this carbonate is an alkylphenol or (In the above general formula, M is 1 or more, for example 1 to 4
It is preferably derived from a bridged phenol, including a linking group of carbon or sulfur atoms, with R ₇ as defined above. Again, the carbonates used can be any of the known neutral or basic compounds. When the anion is borate, sulfate or phosphate, R ₇ may also be an alkoxylated chain. Examples of such compounds in the case of sulfates include (R ₈ -(OCH ₂ CH ₂ ) _o -O) groups and in the case of phosphates and borates (R ₈ -(OCH ₂ CH ₂ ) _o -O ₂ groups, where R ₈
The total carbon content of is the same as defined as R ₅ above. The cations of these salts preferably have the formula R ₆ ZH ₃ ⁺ ; (R ₆ ) ₂ ZH ₂ ⁺ ; (R ₆ ) ₃ ZH ⁺ ; (R ₆ ) ₄ Z ⁺ where R ₆ is a hydrocarbyl group. , preferably an alkyl group) or a sulfonium ion.
If the cation contains more than one such group, the groups may be the same or different and Z is nitrogen or phosphorus. It is preferred that R ₆ contains 4 to 30 carbon atoms, more preferably 14 to 20 carbon atoms, and it is also preferred that R ₆ consists of a straight chain alkyl group. Examples of suitable alkyl groups include methyl, ethyl, propyl, n-octyl, n-dotecyl, n-
- Includes tridecyl, _C13 oxo, coco, hydrogenated tallow, behenyl, lauryl. The R ₆ group may be substituted, for example with hydroxy or amino groups (as in polyamines, for example). In another embodiment, a cationic hydrocarbyl group can confer oil solubility, such as in salts of fatty amines, such as hydrogenated tallow amine. Derivatives of alkyl-substituted dicarboxylic acids or anhydrides can also be used as polar compounds. For example, the general formula [In the above general formula, at least one of R ₉ or R ₁₀
pieces are long chains (e.g. 10-120 pieces, preferably 12-100 pieces)
an alkyl or alkenyl group (of 5 carbon atoms),
For example polyisobutylene or polypropylene. The other R ₉ or R ₁₀ may be the same,
Alternatively, it may be hydrogen. P and Q may be the same or different and may be hydroxy or alkoxy groups or may together form an anhydride ring. Succinic acid derivatives may also be used. can. In another less preferred embodiment, the cation may be a metal cation, in which case the metal is preferably an alkali metal such as sodium or potassium or an alkaline earth metal such as barium, calcium or magnesium. be. Although the ionic compounds described above are the preferred polar oil-soluble compounds of the present invention, the inventors have found that polar nonionic compounds are also effective. For example, a primary amine of formula R ₁₁ −NH ₂ , formula (R ₁₁ ) ₂ NH
Secondary amines of and primary alcohols of formula R ₁₁ -OH can be used provided they are oil-soluble, for which R ₁₁ preferably contains at least 8 carbon atoms and is non-ionic. Preferably the compounds have a carbon content as defined above as R ₅ . Nitrogen compounds are polar compounds that are particularly effective in keeping the wax crystals separate from each other, i.e. in preventing agglomeration of the wax crystals, and are preferred component (C) of the additive mixture of the present invention. It is. Examples of suitable compounds include oil-soluble ammonium salts, amines, commonly prepared by reaction of at least 1 molar ratio of amines with 1 molar ratio of hydrocarbylic acids or anhydrides thereof having 1 to 4 carboxylic acid groups. Includes salts and/or imides. In the case of polycarboxylic acids or their anhydrides,
All acid groups may be converted to amine salts or amides, or a portion of the acid groups may be converted to esters by reaction with hydrocarbyl alcohols,
Alternatively, it may be left unreacted. An example of a suitable amide is the amide of succinic acid described in GB 1140771. The hydrocarbyl groups of the above nitrogen compounds may be straight-chain or branched, saturated or unsaturated, aliphatic or cycloaliphatic or aryl or alkaryl, with long chains, e.g. _C12 - _C40 , preferably _C14 -C _{twenty four}
It is. However, short chains can be included, such as _C1 to _C11 , provided that the total number of carbons in the compound is sufficient for solubility in distillate fuel oil. For oil solubility, the total carbon atoms generally range from 30 to 300, e.g.
Although 160 carbon atoms is sufficient, the number of carbon atoms required varies depending on the polarity of the compound. It is also preferred that the compound contains at least one straight chain alkyl segment containing 8 to 40, preferably 12 to 30 carbon atoms. This linear alkyl segment may be in one amine or ammonium ion, or in several amines or ammonium ions, or in an acid, or in an alcohol (if an ester group is also present). ). It is necessary that at least one ammonium salt, or amine salt, or amide bond be present in the molecule. Hydrocarbyl groups can include hydroxy groups, carbonyl groups, ester groups, or other groups or atoms such as oxygen or sulfur or chlorine atoms. Amines that can be reacted with the carboxylic acid include primary, secondary, tertiary or quaternary amines, preferably secondary amines. If an amide is to be made, a primary or secondary amine is used. Examples of primary amines include n-dodecylamine, n-tridecylamine, _C13 oxoamine,
Includes cocoa amine, tallow amine, and behenyl amine. Examples of secondary amines include methyl-
Included are laurylamine, dodecyl-octylamine, coco-methylamine, tallow-methylamine, methyl-n-octylamine, methyl-n-dodecylamine, methyl-behenylamine and dihydrogenated tallow amine. Examples of tertiary amines include:
Coco-diethylamine, cyclohexyl-diethylamine, coco-dimethylamine, methyl-seryl-stearylamine, methyl-ethyl-cocoamine, methyl-cetyl-stearylamine, and the like. Examples of quaternary ammonium cations or salts include dimethyldicetylammonium and dimethyldistearylammonium chloride. Amine mixtures can also be used, and many amines derived from natural products are mixtures. Thus, cocoa amine derived from coconut oil has C ₈ ~
It is a mixture of primary amines with straight chain alkyl groups in the C ₁₈ range. Another example is hydrogenated tallow amine derived from tallow acid;
Contains a mixture of _C14 to _C18 straight chain alkyl groups. Hydrogenated tallow amine is particularly preferred. Examples of carboxylic acids or anhydrides include formic acid,
Acetic acid, hexanoic acid, lauric acid, myristic acid,
Palmitic acid, hydroxystearic acid, behenic acid, naphthenic acid, salicylic acid, linoleic acid, dilinoleic acid, trilinoleic acid, maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, the aforementioned alkenylsuccinic anhydride, Adipic acid, glutaric acid, sebacic acid, lactic acid, malic acid, malonic acid, citraconic acid, phthalic acid (ortho or meta or para) such as terephthalic acid,
Phthalic anhydride, citric acid, gluconic acid, tartaric acid,
These include 9,10-dihydroxystearic acid and cyclohexane-1,2-dicarboxylic acid. Particular examples of alcohols that can also be reacted with acids include 1-tetradecanol, _C13 - _C18 oxo alcohols prepared from mixtures of cracked waxy olefins, 1-hexadecanol, 1-octadecanol, Included are behenyl alcohol, 1,2-dihydroxyoctadecane and 1,10-dihydroxydecane. Amides can be prepared in a conventional manner by heating a primary or secondary amine and an acid or acid anhydride. Similarly, esters can be made by partially esterifying an acid or anhydride by heating an alcohol and a polycarboxylic acid (so that at least one carboxyl group remains for reaction with an amine to form an amide or amine salt). Manufactured in the usual manner by Alkylammonium salts are also prepared by mixing an amine (or ammonium hydroxide) with an acid or acid anhydride, or a partial ester of a polycarboxylic acid, or a partial amide of a polycarboxylic acid, with stirring, and generally by heating gently (e.g. ~80°C) by simple mixing. Particularly preferred are nitrogen compounds of the type mentioned above prepared from dicarboxylic acids. Most preferred are mixed amine salts/amides, which are prepared by heating maleic anhydride, alkenylsuccinic anhydride or phthalic acid or phthalic anhydride with a secondary amine, preferably hydrogenated tallow amine, at mild temperatures (e.g. 60°C). It can be manufactured by The addition of (C) can reduce the size of wax crystals and reduce the rate at which wax settles out of fuels containing only distillate flow improvers. We believe that the presence of these polar compounds is beneficial under normal fuel storage conditions, when the fuel is stored at low temperatures for long periods of time and when its temperature is increased very gradually (i.e., about 0.3°C/
found that it is effective even when lowered (time). Distillate fuel oils for which the additive formulations of the present invention are particularly useful generally have boiling points between 120 and 500°C, such as between 160 and 400°C.
It is ℃. The fuel oil may consist of an atmospheric distillate or a vacuum distillate, or a blend of cracked gas oil or straight run and pyrolysis and/or catalytic cracking distillates in any ratio. The most common petroleum distillate fuel oils are kerosene, jet fuel, diesel fuel and heating oil. The heating oil can be either a straight distillate oil or a cracked gas oil or a blend of both. The cold flow problems alleviated by the use of the additive formulations of the present invention are most commonly encountered with diesel fuels and heating oils. Recently, there has been a trend to increase the final boiling point (FBP) of distillate oils to maximize fuel yield. However, these fuels contain long chain paraffins in the fuel and therefore generally have high cloud points. This also exacerbates the difficulties these fuels encounter in cold climates and increases the need to add flow improving additives. We have found that the additive formulations of the present invention are particularly useful in these fuels. As used herein, oil-soluble means that the additive is soluble in the fuel at ambient temperature, e.g., at least 0.1% by weight in fuel oil at 25°C, but at least A portion of the agent precipitates out of solution near the cloud point to control the wax crystals that form. EXAMPLES Hereinafter, the present invention will be explained with reference to Examples, but these Examples are not intended to limit the present invention. In these examples, the distillate oil flow improvers used
A1 has two different oil solubility such that one acts primarily as a wax growth inhibitor and the other as a nucleating agent as described in UK Patent No. 1374051.
Seed ethylene-vinyl acetate copolymer mixture approx.
Concentrate in 50% by weight aromatic diluent. More specifically, the two polymers contain 75% by weight wax growth inhibitor.
and a nucleating agent in a proportion of about 25% by weight. The wax growth inhibitor consists of ethylene and about 38% by weight vinyl acetate and has a number average molecular weight of about 1800 (VPO). This wax growth inhibitor is covered by the above-mentioned British patent.
Copolymer B of Example 1 (No. 8
column, lines 25-35). The nucleating agent consists of ethylene and about 16% by weight vinyl acetate and has a number average molecular weight of about 3000 (VPO). This nucleating agent is described in GB 1374051 as Copolymer H (see columns 7-8, table). Distillate flow improver A2 is a separately used wax growth inhibiting component of A1. Hydrocarbon polymer B1, useful as a lubricating oil viscosity index (VI) improver, contains 44% by weight ethylene and has a number average molecular weight (by membrane osmometry) of approximately 35,000 to 40,000.
It is a copolymer of ethylene and propylene that is substantially linear and produced using a Ziegler-Natsuta catalyst. The polar compounds used were as follows. C1: Half-amide/semi-alkylammonium salt obtained by reaction of 2 moles of di-[hydrogenated tallow]-amine with 1 mole of phthalic anhydride. C2: Diamide obtained by dehydrating C1. C3: Citric acid triamide obtained by dehydrating the reaction product of 3 moles of di[hydrogenated tallow]-amine and 1 mole of citric acid. The fuels tested with additives are shown in the table below.

[Table] The initial response of oil to additives is “journal.
of. The. Instate. of. Petroleum (Journal of the Institute of
Petroleum)”, Volume 52, No. 510, June 1966, 173
Cold performed in the manner described in detail on pages ~185. Filter. Plugging. point. Test (Cold Filter Plugging Point
Test) (CFPPT). in short,
A 40 ml sample of the oil to be tested is cooled in a bath maintained at approximately -34°C. Periodically (starting at least 2°C above the cloud point and each time the temperature decreases by 1°C), the test device, which is a pipette with an overturned funnel attached to its lower end, is placed below the surface of the oil to be tested for a specified period of time. The ability of cooled test oil to flow through a fine screen is tested. Line the mouth of the funnel with a 350 mesh screen with an area defined by 12 mm in diameter. Each cycle involves applying a vacuum to the top of the pipette and drawing the oil through the screen to the 20 ml mark. After passing this test, immediately reapply the oil each time.
Return to CFPP pipe. Repeat this test for each 1°C decrease in temperature until oil no longer fills the pipette within 60 seconds. Record this temperature as the CFPP temperature. Another measurement of additive performance is made under slower, more natural cooling. The performance of these additives in the above fuels was evaluated by two types of Filter Screen analysis under different cooling conditions.
Analysis) (FSA). Cool a 100g sample of FSA1 fuel under specified conditions (below). The resulting sample is shaken to homogenize the wax in the fuel suspension. Pour 40 ml of this suspension into a pour point tube, and place a filter screen (approximately 1 cm in diameter) at the bottom end.
20 with below mesh round screen
ml pipette into this pour point tube. The wax-clouded fuel is then sucked (under suction pressure of 20 cm of water) into the pipette through the filter screen. The sample passes if the pipette fills in less than 30 seconds; otherwise it fails. Cool 300g of FAS2 fuel sample under specified conditions (below). Approximately 20 ml of the surface fuel layer of the resulting sample is removed by suction to ensure that the test is not influenced by unusually large wax crystals that tend to form on the surface during cooling. The sample free of surface crystals is then shaken to homogenize the wax in the fuel suspension. Place a pipette with a filter screen similar to that described in FSA1 and also connected to a 250 ml graduated cylinder into the sample, then pour all the fuel (with suction pressure of 30 cm of water) through the filter screen and through the pipette into the graduated cylinder. Suction inside. If all the fuel is aspirated in 60 seconds, the sample is said to have passed the filter screen. 20, 30, 40, 60, 80, 100, 120, 150, 200,
Using a pipette with a filter screen of mesh numbers 250 and 300, determine the minimum mesh (maximum number) through which the fuel will pass. The cooling methods used in the test are summarized in the table below. The letters in the table are used in each example to indicate which cooling method was used prior to testing.

TABLE The following examples describe the performance of fuels containing various additive packages. Although each component may have been used as a solution in an inert diluent, all numbers in Examples 1-5 are actual additive concentrations in ppm of active ingredient. Example 1 The results obtained are as follows.

【table】

[Table] Agent Polymer Material

Claims (1)

[Scope of Claims] 1. An additive formulation containing substances of the following classes (A), (B) and (C). (A) General formula (In the above general formula, R ₁ is methyl or hydrogen, R ₂ is -OOCR ₄ or -COOR ₄ ,
where R ₄ is a C ₁ -C ₂₈ alkyl group and R ₃ is hydrogen or -COOR ₄ 500~50000
An oil-soluble ethylene backbone polymer for distillate oil flow improvement having a number average molecular weight in the range of . (B) A hydrocarbon polymer or derivative thereof having a number average molecular weight of 10 ⁴ or more. (C) unlike (A) and (B), containing a total of 30 to 300 carbon atoms, having at least one straight chain alkyl segment of 8 to 40 carbons and having 1 to 4 carbon atoms;
A polar oil-soluble nitrogen compound of formula RX selected from the group consisting of amine salts and/or amides of hydrocarbyl carboxylic acids or anhydrides thereof having 3 carbonyl groups. 2. The additive formulation according to claim 1, wherein the ethylene backbone polymer is a copolymer of ethylene and vinyl acetate. 3. Any one of claims 1 to 2, wherein the hydrocarbon polymer is an olefin copolymer.
Additive formulations as described in Section. 4. Additive formulation according to claim 3, wherein the hydrocarbon polymer is a copolymer of ethylene and propylene. 5. The additive formulation according to claim 3 or 4, wherein the hydrocarbon polymer is an olefin copolymer derivative. 6 Claims in which the nitrogen compound (C) is phthalic acid or phthalic anhydride in which both carboxylic acid groups have been reacted with a secondary alkyl monoamide having an alkyl group of essentially 14 to 18 carbon atoms. The additive formulation according to claim 1. 7. An additive formulation comprising 70 to 20% by weight of an additive formulation containing substances of the following classes (A), (B) and (C) and 30 to 80% by weight of a hydrocarbon diluent. (A) General formula (In the above general formula, R ₁ is methyl or hydrogen, R ₂ is -OOCR ₄ or -COOR ₄ ,
where R ₄ is a C ₁ -C ₂₈ alkyl group and R ₃ is hydrogen or -COOR ₄ 500~50000
An oil-soluble ethylene backbone polymer for distillate oil flow improvement having a number average molecular weight in the range of . (B) A hydrocarbon polymer or derivative thereof having a number average molecular weight of 10 ⁴ or more. (C) unlike (A) and (B), containing a total of 30 to 300 carbon atoms, having at least one straight chain alkyl segment of 8 to 40 carbons and having 1 to 4 carbon atoms;
A polar oil-soluble nitrogen compound of formula RX selected from the group consisting of amine salts and/or amides of hydrocarbyl carboxylic acids or anhydrides thereof having 3 carbonyl groups. 8. A fuel composition comprising a distillate fuel oil and 0.001 to 0.5% by weight of an additive formulation containing substances of the following classes (A), (B) and (C). (A) General formula (In the above general formula, R ₁ is methyl or hydrogen, R ₂ is -OOCR ₄ or -COOR ₄ ,
where R ₄ is a C ₁ -C ₂₈ alkyl group and R ₃ is hydrogen or -COOR ₄ 500~50000
An oil-soluble ethylene backbone polymer for distillate oil flow improvement having a number average molecular weight in the range of . (B) A hydrocarbon polymer or derivative thereof having a number average molecular weight of 10 ⁴ or more. (C) unlike (A) and (B), containing a total of 30 to 300 carbon atoms, having at least one straight chain alkyl segment of 8 to 40 carbons and having 1 to 4 carbon atoms;
A polar oil-soluble nitrogen compound of formula RX selected from the group consisting of amine salts and/or amides of hydrocarbyl carboxylic acids or anhydrides thereof having 3 carbonyl groups. 9. Claim 8, wherein the additive formulation contains 1 part by weight of a substance of class (A), 0.1 to 5 parts by weight of a substance of class (B), and 0.2 to 10 parts by weight of a substance of class (C). The fuel composition described in Section. 10 Middle distillate fuel oil containing an additive formulation containing substances of the following classes (A), (B) and (C). (A) General formula (In the above general formula, R ₁ is methyl or hydrogen, R ₂ is -OOCR ₄ or -COOR ₄ ,
where R ₄ is a C ₁ -C ₂₈ alkyl group and R ₃ is hydrogen or -COOR ₄ 500~50000
An oil-soluble ethylene backbone polymer for distillate oil flow improvement having a number average molecular weight in the range of . (B) A hydrocarbon polymer or derivative thereof having a number average molecular weight of 10 ⁴ or more. (C) unlike (A) and (B), containing a total of 30 to 300 carbon atoms, having at least one straight chain alkyl segment of 8 to 40 carbons and having 1 to 4 carbon atoms;
A polar oil-soluble nitrogen compound of formula RX selected from the group consisting of amine salts and/or amides of hydrocarbyl carboxylic acids or anhydrides thereof having 3 carbonyl groups. 11 The ethylene main chain polymer is a copolymer of 4 to 20 moles of ethylene and 1 mole of vinyl acetate,
Distillate fuel oil according to claim 10, having a number average molecular weight in the range of 1000 to 6000. 12. The distillate according to claim 10 or 11, wherein the hydrocarbon polymer is an olefin copolymer of two or more C2 _{- C30} olefins, and the copolymer has a molecular weight of 10,000 or more. Output fuel oil. 13. The distillate fuel oil of claim 12, wherein the hydrocarbon polymer is a copolymer of ethylene and propylene useful as a viscosity index improver for lubricating oils. 14. The distillate fuel oil according to claim 12, wherein the hydrocarbon polymer is polyisobutylene. 15. Distillate fuel according to claim 10, wherein the nitrogen compound (C) is essentially phthalic acid or phthalic anhydride reacted with a secondary alkylamine having an alkyl group of 14 to 18 carbon atoms. oil. 16. The distillate fuel oil of claim 10, wherein the nitrogen compound is essentially citric acid reacted with a secondary alkylamine having an alkyl group of 14 to 18 carbon atoms. 17 Nitrogen compound is essentially 14 with maleic anhydride
11. The distillate fuel oil of claim 10, which is the reaction product of a secondary alkylamine having an alkyl group of ~18 carbon atoms.